Ultrasmall and Highly Dispersed Pt Entities Deposited on Mesoporous N-doped Carbon Nanospheres by Pulsed CVD for Improved HER.

Vapor-based deposition techniques are emerging approaches for the design of carbon-supported metal powder electrocatalysts with tailored catalyst entities, sizes, and dispersions. Herein, a pulsed CVD (Pt-pCVD) approach is employed to deposit different Pt entities on mesoporous N-doped carbon (MPNC) nanospheres to design high-performance hydrogen evolution reaction (HER) electrocatalysts. The influence of consecutive precursor pulse number (50-250) and deposition temperature (225-300 °C) are investigated. The Pt-pCVD process results in highly dispersed ultrasmall Pt clusters (≈1 nm in size) and Pt single atoms, while under certain conditions few larger Pt nanoparticles are formed. The best MPNC-Pt-pCVD electrocatalyst prepared in this work (250 pulses, 250 °C) reveals a Pt HER mass activity of 22.2 ± 1.2 A mg-1 Pt at -50 mV versus the reversible hydrogen electrode (RHE), thereby outperforming a commercially available Pt/C electrocatalyst by 40% as a result of the increased Pt utilization. Remarkably, after optimization of the Pt electrode loading, an ultrahigh Pt mass activity of 56 ± 2 A mg-1 Pt at -50 mV versus RHE is found, which is among the highest Pt mass activities of Pt single atom and cluster-based electrocatalysts reported so far.

Ultrascaled Contacts to Monolayer MoS2 Field Effect Transistors.

Two-dimensional (2D) semiconductors possess promise for the development of field-effect transistors (FETs) at the ultimate scaling limit due to their strong gate electrostatics. However, proper FET scaling requires reduction of both channel length (LCH) and contact length (LC), the latter of which has remained a challenge due to increased current crowding at the nanoscale. Here, we investigate Au contacts to monolayer MoS2 FETs with LCH down to 100 nm and LC down to 20 nm to evaluate the impact of contact scaling on FET performance. Au contacts are found to display a ∼2.5× reduction in the ON-current, from 519 to 206 µA/µm, when LC is scaled from 300 to 20 nm. It is our belief that this study is warranted to ensure an accurate representation of contact effects at and beyond the technology nodes currently occupied by silicon.

Electron beam evaporated Au islands as a nanoscale etch mask on few-layer MoS2 and fabrication of top-edge hybrid contacts for field-effect transistors.

Metal contacts to two-dimensional layered semiconductors are crucial to the performance of field-effect transistors (FETs) and other applications of layered materials in nanoelectronics and beyond. In this work, the wetting behavior of very thin Au films on exfoliated MoS2 flakes was studied and evaluated as a nanoscale, self-assembled dry etch mask. Etching nanoscale pits into MoS2 flakes prior to metallization from the top of the flake forms edge sites that contribute some fraction of edge contacts in addition to top contacts for additional carrier injection and lower contact resistance. The morphology and thickness of Au islands and MoS2 were studied with scanning electron microscopy and atomic force microscopy before and after etching with low-power plasmas. A Cl2 plasma etch of 10 s with a Au island mask of 6 nm (nominal) showed the best resulting morphology among the plasma conditions studied. Back-gated MoS2-based FETs on SiO2/p +-Si with Ti/Au contacts were fabricated using a Cl2 etch of only the contact regions, and they yielded devices with ON currents of 100s µA/µm, ON/OFF ratios ⩾106, and contact resistance <10 kΩ µm. The best set of devices had a very low contact resistance of ∼1 kΩ µm with almost no dependence of contact resistance on gating. Using nanoscale etch masks made from metal islands could be highly customizable and shows promise for engineering FETs with low contact resistance.

Uncovering the Effects of Metal Contacts on Monolayer MoS2.

Metal contacts are a key limiter to the electronic performance of two-dimensional (2D) semiconductor devices. Here, we present a comprehensive study of contact interfaces between seven metals (Y, Sc, Ag, Al, Ti, Au, Ni, with work functions from 3.1 to 5.2 eV) and monolayer MoS2 grown by chemical vapor deposition. We evaporate thin metal films onto MoS2 and study the interfaces by Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and electrical characterization. We uncover that (1) ultrathin oxidized Al dopes MoS2 n-type (>2 × 1012 cm-2) without degrading its mobility, (2) Ag, Au, and Ni deposition causes varying levels of damage to MoS2 (e.g. broadening Raman E' peak from <3 to >6 cm-1), and (3) Ti, Sc, and Y react with MoS2. Reactive metals must be avoided in contacts to monolayer MoS2, but control studies reveal the reaction is mostly limited to the top layer of multilayer films. Finally, we find that (4) thin metals do not significantly strain MoS2, as confirmed by X-ray diffraction. These are important findings for metal contacts to MoS2 and broadly applicable to many other 2D semiconductors.

Enhanced thermoelectric efficiency in nanocrystalline bismuth telluride nanotubes.

We report on the thermal and thermoelectric properties of individual nanocrystalline Bi2 Te3 nanotubes synthesized by the solution phase method using 3ω method and a microfabricated testbench. Measurements show that the nanotubes offer improved ZT compared to bulk Bi2Te3 near room temperature due to an enhanced Seebeck coefficient and suppressed thermal conductivity. This improvement in ZT originates from the nanocrystalline nature and low dimensionality of the nanotubes. Domain boundary filtering of low-energy electrons provides an enhanced Seebeck coefficient. The scattering of phonons at the surface of the nanotube leads to suppressed thermal conductivity. These have been theoretically analyzed using the Boltzmann equation based on the relaxation time approximation and Landauer approach. This work clearly demonstrates the possibility of achieving enhancement in thermoelectric efficiency by combining nanocrystalline and low-dimensional systems.

Achieving Minimal Heat Conductivity by Ballistic Confinement in Phononic Metalattices.

Controlling the thermal conductivity of semiconductors is of practical interest in optimizing the performance of thermoelectric and phononic devices. The insertion of inclusions of nanometer size in a semiconductor is an effective means of achieving such control; it has been proposed that the thermal conductivity of silicon could be reduced to 1 W/m/K using this approach and that a minimum in the heat conductivity would be reached for some optimal size of the inclusions. Yet the experimental verification of this design rule has been limited. In this work, we address this question by studying the thermal properties of silicon metalattices that consist of a periodic distribution of spherical inclusions with radii from 7 to 30 nm, embedded into silicon. Experimental measurements confirm that the thermal conductivity of silicon metalattices is as low as 1 W/m/K for silica inclusions and that this value can be further reduced to 0.16 W/m/K for silicon metalattices with empty pores. A detailed model of ballistic phonon transport suggests that this thermal conductivity is close to the lowest achievable by tuning the radius and spacing of the periodic inhomogeneities. This study is a significant step in elucidating the scaling laws that dictate ballistic heat transport at the nanoscale in silicon and other semiconductors.

Novel Sn-Based Contact Structure for GeTe Phase Change Materials.

Germanium telluride (GeTe) is a phase change material (PCM) that has gained recent attention because of its incorporation as an active material for radio frequency (RF) switches, as well as memory and novel optoelectronic devices. Considering PCM-based RF switches, parasitic resistances from Ohmic contacts can be a limiting factor in device performance. Reduction of the contact resistance ( Rc) is therefore critical for reducing the on-state resistance to meet the requirements of high-frequency RF applications. To engineer the Schottky barrier between the metal contact and GeTe, Sn was tested as an interesting candidate to alter the composition of the semiconductor near its surface, potentially forming a narrow band gap (0.2 eV) SnTe or a graded alloy with SnTe in GeTe. For this purpose, a novel contact stack of Sn/Fe/Au was employed and compared to a conventional Ti/Pt/Au stack. Two different premetallization surface treatments of HCl and deionized (DI) H2O were employed to make a Te-rich and Ge-rich interface, respectively. Contact resistance values were extracted using the refined transfer length method. The best results were obtained with DI H2O for the Sn-based contacts but HCl treatment for the Ti/Pt/Au contacts. The as-deposited contacts had the Rc (ρc) of 0.006 Ω·mm (8 × 10-9 Ω·cm2) for Sn/Fe/Au and 0.010 Ω·mm (3 × 10-8 Ω·cm2) for Ti/Pt/Au. However, the Sn/Fe/Au contacts were thermally stable, and their resistance decreased further to 0.004 Ω·mm (4 × 10-9 Ω·cm2) after annealing at 200 °C. In contrast, the contact resistance of the Ti/Pt/Au stack increased to 0.012 Ω·mm (4 × 10-8 Ω·cm2). Transmission electron microscopy was used to characterize the interfacial reactions between the metals and GeTe. It was found that formation of SnTe at the interface, in addition to Fe diffusion (doping) into GeTe, is likely responsible for the superior performance of Sn/Fe/Au contacts, resulting in one of the lowest reported contact resistances on GeTe.

Confined Chemical Fluid Deposition of Ferromagnetic Metalattices.

A magnetic, metallic inverse opal fabricated by infiltration into a silica nanosphere template assembled from spheres with diameters less than 100 nm is an archetypal example of a "metalattice". In traditional quantum confined structures such as dots, wires, and thin films, the physical dynamics in the free dimensions is typically largely decoupled from the behavior in the confining directions. In a metalattice, the confined and extended degrees of freedom cannot be separated. Modeling predicts that magnetic metalattices should exhibit multiple topologically distinct magnetic phases separated by sharp transitions in their hysteresis curves as their spatial dimensions become comparable to and smaller than the magnetic exchange length, potentially enabling an interesting class of "spin-engineered" magnetic materials. The challenge to synthesizing magnetic inverse opal metalattices from templates assembled from sub-100 nm spheres is in infiltrating the nanoscale, tortuous voids between the nanospheres void-free with a suitable magnetic material. Chemical fluid deposition from supercritical carbon dioxide could be a viable approach to void-free infiltration of magnetic metals in view of the ability of supercritical fluids to penetrate small void spaces. However, we find that conventional chemical fluid deposition of the magnetic late transition metal nickel into sub-100 nm silica sphere templates in conventional macroscale reactors produces a film on top of the template that appears to largely block infiltration. Other deposition approaches also face difficulties in void-free infiltration into such small nanoscale templates or require conducting substrates that may interfere with properties measurements. Here we report that introduction of "spatial confinement" into the chemical fluid reactor allows for fabrication of nearly void-free nickel metalattices by infiltration into templates with sphere sizes from 14 to 100 nm. Magnetic measurements suggest that these nickel metalattices behave as interconnected systems rather than as isolated superparamagnetic systems coupled solely by dipolar interactions.

Cosputtered Calcium Manganese Oxide Electrodes for Water Oxidation.

Calcium manganese oxide films were prepared by cosputter deposition from Mn and CaMnO3 targets and evaluated for their suitability as catalysts for the oxygen evolution reaction (OER). Scanning electron microscopy (SEM) revealed a compact morphology for the as-deposited films and the formation of nanorodlike features on the surfaces after annealing at 600 °C. X-ray-photoelectron-spectroscopy analysis showed that the surface oxidation state is close to +III (as in Mn2O3) for the as-deposited films and increases slightly to a mixture of III and IV after annealing occurs in dry air at 400-600 °C. Glancing-incidence X-ray diffraction (GIXRD) suggested that the CaMnxOy films are amorphous even when heated to 600 °C. However, transmission electron microscopy (TEM) showed that there is actually a polycrystalline component of the film, which best matches Mn3O4 (hausmannite with the average Mn oxidation state of ∼+2.7) but may have a slightly expanded unit cell because of the incorporation of Ca. Electrochemical analyses revealed that the as-deposited CaMnxOy films were OER-inactive. In contrast, annealing at 400 or 600 °C resulted in an increase of ∼15-fold in the current densities, which reached j ≅ 1.5 mA·cm-2 at OER overpotentials of η ≈ 550 mV in cyclic voltammetry (CV) sweeps. For the same η, annealed CaMnxOy electrodes also showed good electrochemical stabilities during 2 h of electrolysis, as rather constant steady-state current densities of j ≅ 0.4-0.5 mA·cm-2 were observed. The thicknesses and surface morphologies of the CaMnxOy films did not change during the electrochemical measurements, indicating that corrosion was negligible. In comparison with a previous study in which Ca-free thin layers of MnOx were evaluated, the results demonstrate that Ca2+ incorporation can enhance the OER activity of MnOx electrocatalysts prepared by sputter deposition. This work provides guidance for designing new electrodes for water oxidation on the basis of the abundant and nontoxic elements manganese and calcium.

Impact of Premetallization Surface Preparation on Nickel-based Ohmic Contacts to Germanium Telluride: An X-ray Photoelectron Spectroscopic Study.

Surfaces of polycrystalline α-GeTe films were studied by X-ray photoelectron spectroscopy (XPS) after different treatments in an effort to understand the effect of premetallization surface treatments on the resistance of Ni-based contacts to GeTe. UV-O3 is often used to remove organic contaminants after lithography and prior to metallization; therefore, UV-O3 treatment was used first for 10 min prior to ex situ treatments, which led to oxidation of both Ge and Te to GeOx (x < 2) and TeO2, respectively. Then the oxides were removed by deionized (DI) H2O, (NH4)2S, and HCl treatments. Additionally, in situ Ar+ ion etching was used to clean the GeTe surface without prior UV-O3 treatment. Ar+ ion etching, H2O, and (NH4)2S treatments create a surface richer in Ge compared to the HCl treatment, after which the surface is Te-rich. However, (NH4)2S also oxidizes Ge and gradually etches the GeTe film. All treated surfaces showed poor stability upon prolonged exposure to air, revealing that even (NH4)2S does not passivate the GeTe surface. The refined transfer length method (RTLM) was used to measure the contact resistance (Rc) of as-deposited Ni-based contacts to GeTe as a function of premetallization surface preparation. HCl-treated samples had the highest Rc (0.036 ± 0.002 Ω·mm), which was more than twice that of the other surface treatments. This increase in Rc is attributed to formation of the Ni1.29Te phase at the Ni/GeTe interface due to an abundance of Te at the surface after HCl treatment. In general, treatments that resulted in Ge-rich surfaces offered lower Rc.

Local electrode atom probe analysis of silicon nanowires grown with an aluminum catalyst.

Local electrode atom probe (LEAP) tomography of Al-catalyzed silicon nanowires synthesized by the vapor­liquid­solid method is presented. The concentration of Al within the Al-catalyzed nanowire was found to be 2 × 10(20) cm(-3), which is higher than the expected solubility limit for Al in Si at the nanowire growth temperature of 550°C. Reconstructions of the Al contained within the nanowire indicate a denuded region adjacent to the Al catalyst/Si nanowire interface, while Al clusters are distributed throughout the rest of the silicon nanowire.

Nonradiative energy transfer between colloidal quantum dot-phosphors and nanopillar nitride LEDs.

We present in this communication our study of the nonradiative energy transfer between colloidal quantum dot (QD) phosphors and nitride nanopillar light emitting diodes (LEDs). An epitaxial p-i-n InGaN/GaN multiple quantum-well (QW) heterostructure was patterned and dry-etched to form dense arrays of nanopillars using a novel etch mask consisting of self-assembled In3Sn clusters. Colloidal QD phosphors have been deposited into the gaps between the nanopillars, leading to sidewall coupling between the QDs and InGaN QW emitters. In this approach, close QW-QD contact and a low-resistance design of the LED contact layer were achieved simultaneously. Strong non-radiative energy transfer was observed from the InGaN QW to the colloidal QD phosphors, which led to a 263% enhancement in effective internal quantum efficiency for the QDs incorporated in the nanopillar LEDs, as compared to those deposited over planar LED structures. Time-resolved photoluminescence was used to characterize the energy transfer process between the QW and QDs. The measured rate of non-radiative QD-QW energy-transfer agrees well with the value calculated from the quantum efficiency data for the QDs in the nanopillar LED.

Lasing from colloidal InP/ZnS quantum dots.

High-quality InP/ZnS core-shell nanocrystal quantum dots (NQDs) were synthesized as a heavy-metal-free alternative to the gain media of cadmium-based colloidal nanoparticles. Upon UV excitation, amplified spontaneous emission (ASE) and optical gain were observed, for the first time, in close-packed InP/ZnS core-shell NQDs. The ASE wavelength can be selected by tailoring the nanocrystal size over a broad range of the spectrum. Moreover, the optical gain profile of InP/ZnS NQDs was matched to the second order feedback of holographic polymer-dispersed liquid crystal gratings, leading to the very first demonstration of an optically-pumped, nanocrystal laser based on InP/ZnS core-shell NQDs.

Employing heavy metal-free colloidal quantum dots in solution-processed white light-emitting diodes.

We report in this communication the design and fabrication of solution-processed white light-emitting diodes (LEDs) containing a bilayer of heavy metal-free colloidal quantum dots (QDs) and polymer in the device active region. White electroluminescence was obtained in the LEDs by mixing the red emission of ZnCuInS/ZnS core/shell QDs and the blue-green emission of poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine). A high color rendering index of 92 was achieved as compared to a 5310 K blackbody reference by virtue of broadband emission of the QDs. The Commission Internationale de l'Eclairage chromaticity coordinates of the white LED output exhibit a distinctive bias dependence. Finally, aging of the white LEDs was studied, revealing the difference between the photochemical stabilities of the QDs and polymer molecules and the consequent effect on the color evolution of the LEDs.

Fabrication and electrical properties of si nanowires synthesized by Al catalyzed vapor-liquid-solid growth.

The synthesis of epitaxially oriented Si nanowires at high growth rates (>1 microm/min) was demonstrated on (111) Si substrates using Al as the catalyst. The use of high H(2) and SiH(4) partial pressures was found to be effective at reducing problems associated with Al oxidation and nanowire nucleation, enabling growth of high aspect ratio structures at temperatures ranging from 500 to 600 degrees C with minimal tapering of the diameter. Because of the high growth rate observed, the Al catalyst is believed to be in the liquid state during the growth. Four-point resistance measurements and back-gated current-voltage measurements indicate that the wires are p-type with an average resistivity of 0.01 +/- 0.004 Omega-cm. These results suggest that Al is incorporated into the Si nanowires under these conditions at concentrations higher than the solubility limit (5-6 x 10(18) cm(-3)) for Al in Si at 550 degrees C. This work demonstrates that Al can serve as both an effective catalyst and p-type dopant for the growth of Si nanowires.

Two-photon-pumped lasing from colloidal nanocrystal quantum dots.

Upconverted lasing in the nonlinear, two-photon absorption regime has been demonstrated, for the first time to the best of our knowledge in colloidal nanocrystal quantum dots (NQDs). Upon pulse excitation at sub-bandgap photon energies the radiative recombination of excitons in close-packed CdSe/CdS/ZnS core-shell NQDs was found to be sufficiently fast to compete with the intrinsic nonradiative Auger recombination, as confirmed by the presence of a fast decay (approximately 7 ps) in the time-resolved photoluminescence.

In situ axially doped n-channel silicon nanowire field-effect transistors.

Axially doped (n+-p--n+) silicon nanowires were synthesized using the vapor-liquid-solid technique by sequentially modulating the introduction of phosphine to the inlet gas stream during growth from a silane source gas. Top-gate and wrap-around-gate metal oxide semiconductor field-effect transistors that were fabricated after thermal oxidation of the silicon nanowires operate by electron inversion of the p- body segment and have significantly higher on-state current and on-to-off state current ratios than do uniformly p- -doped nanowire field-effect devices. The effective electron mobility of the devices was estimated using a four-point top-gate structure that excludes the source and drain contact resistance and was found to follow the expected universal inversion layer mobility versus effective electric field trend. The field-effect properties of wrap-around-gate devices are less sensitive to global-back-gate bias and thus provide better electrostatic control of the nanowire channel. These results demonstrate the ability to tailor the axial doping profile of silicon nanowires for future planar and vertical nanoelectronic applications.

Bright and color-saturated emission from blue light-emitting diodes based on solution-processed colloidal nanocrystal quantum dots.

We report a multilayer solution-processed blue light-emitting diode based on colloidal core/shell CdS/ZnS nanocrystal quantum dots (QDs). At a low-operating voltage of 5.5 V, the device emits spectrally pure blue radiation at 460 nm with a narrow full-width-at-half-maximum bandwidth of 20 nm and high brightness up to 1600 cd/m2. Broad-band, long-wavelength emission from the polymer components and deep traps in the QDs are minimized to less than 5% of the total emission.

Selective plating for junction delineation in silicon nanowires.

The in situ growth of p-n junctions in silicon nanowires enables the fabrication of a variety of nanoscale electronic devices. We have developed a method for selective coating of Au onto n-type segments of silicon nanowire p-n junctions. Selective plating allows for quick verification of the position of p-n junctions along the nanowire using electron microscopy and allows for measurement of segment length.